Process for the manufacture of valuable products from olefins



Patented Nov. 17, 1942 PROCESS FOR THE MANUF VALUABLE PRODUCTS FROM OLII'INS Ludwig Muller, meld- Riohard Michel and UerdingemGermany erty Custodian ACTUBI F vestedintheAllenrl'or Drawing. application March :0, 1m, Serial No. 132,180. .In Gm M 2, 1,36

5 Claims. (01. zoo-sat) This invention relates to a process for the manufacture of valuable products from oleflns.

In accordance with the invention an olefin is reacted with an unsaturated compound selectedfrom the group consisting of an olefin, an arcthe side chain corresponding to the number of the carbon atoms of the olefin employed. In this matic compound and'a partially hydrogenated aromatic compound in the presence of a compound selected from the group consisting of a hetero-polyacid and an acid salt of a heteropolyacid, i. e;, an acid of this type, part of the acid hydrogen atoms of which are substituted by a metal.

Among the hetero-polyacids found appropriate for the process of the present invention maybe mentioned phosphotungstic acid, phosphomolybdic acid, phospho-molybdic-tungstic acid,

phospho-vanadic acid, silico-molybdic acid, silico tungstic acid, arsenious molybdic acid and borontungstic acid. As already mentioned before instead of these hetero-polyacids acid salts thereof may be employed, for example the acid salts of the hetero-polyacids mentioned before with sodium, potassium, barium, copper, mercury, arsenic and lead.

Among the olefi'ns suitable for the purpos of this invention may be mentioned, for example,

ethylene, propylene, s-butyi, p-butylene, isobutylene, amylene, hexylene, nonylene, dodecyiene, pentadecylene, butadiene, isoprene and cyclic olefins, such as cyclohexene, methyl and dimethyl cyclohexenes and cyclohexadiene.

manner from benzene, naphthalene, anthracene, phenanthrene, pyrene, carbazole, substitution productsof these hydrocarbons, such as toluene, xylene, ethyl bensene, halogenated benzenes, for example chlorobenzene, furthermore methyl naphthalene, isopropyl naphthalene, partially hydrogenated aromatic hydrocarbons, such as tetrahydronaphthalene or substitution products thereof, aromatic hydroxy compounds, such as phenol, cresol, naphthol, phenol others, such as anisole, phenetole, finally aromatic acids, such as salicylic acid and the like, the corresponding alkylation products are obtained.

In general the reaction may be accelerated by I I the addition of a catalyst, especially a heavy metal salt, such as a copper, silver or nickel salt.

.It is by no means necessary for the process of I the invention to employ these olefins in a state. Theymay indeed be used in admixt with one another or with other gases, such as for example, in the form of waste gases derived from cracking processes.

Impurities of the gas mixture, such as for example,' hydrogen sulfide may be removed in any Y known manner before subjecting the gas to the process oi this invention.

when an olefin-as such or inadmixture with 'other olefins is subjected to the action'of' the catalysts referred to, polymerisation products or mixed polymerisation products are obtained.

Furthermore when an olefin as such or in admixture with other olefins is subjected to the compound probably proceeds in such a manner i -gthat at least one alkyl side chain is attached to Ifdesired ,or required the reaction may be performed in the presence of asolvent, which does not react under the reaction conditions, such as for example, in the presence of ligroine, decahydronaphthalene, carbon tetrachloride, chloroform, etc., this method of working being of particular advantage if one of the reaction components is solid under the temperature conditions employed.

The temperature and pressure, at which the condensation is carried out may vary within wide limits. We have obtained good results with temperatures and pressures ansins from above about C. and atmospheric pressure to about 209 C. and the corresponding elevated pressure given by the nature of the reaction material and especially from about to about 200 0., the upper limit for the temperature and the corresponding pressure being only given by the decomposition point of the components of the reaction mixture and by the resistivity of the construction In contradistinction to the known process for the polymerisation of olcflns in the presence of catalysts of the Friedel-Crafts type whereby mainly oils of higher boiling range are obtained, the process of the present invention enables the production of polymerisaiton products of essen-' tially lower boiling range.

con parts by weight of isobutylene added with 100 parts by weight of an acid sodium salt of the nucleus, the number of the carbon atoms of 5s p pho-tunlltic acid in which 3 of the 7 acid hydrogen atoms of the phospho-tungstic acid are substituted by sodium, are stirred at 175 C. for

' 1 hours in a-c'opper autoclave at a pressure 470 parts by weight of phenol are subjected for 2 hours in a copper autoclave at a temperature of 175C. to condensation with isobutylene gas in the presence of 50 parts by weight of phosphotungstic acid. After separating the reaction product from the phospho-tungstic acid and fractionally distilling there is obtained as principal product p-isobutylphenol melting at 99 C. with recovery of unchanged phenol.

Example 3 the main fraction there are obtained 740 parts by weight of a completely colorless isododecyl-phenol, which distillsat 195-200" C. under a pressure of mms. mercury gauge.

. Example 4 504 parts by weight of isononylene of the boiling range 130-l50 C. are condensed by using again the acid sodium salt of phospho-molybdictungstic acid employed in Example 3 with 416 parts by weight of crude cresol (40% phenol, 50%

cresols, 10% xylenols) in a copper autoclave at -170 C. 620. parts by weight of a colorless isononyl- (crudel-cresol product are obtained boiling at -195 C. under a pressure of 15 mms. mercury gauge.

We claim:

1. Process which comprises reacting at a temperature above about 100 C. upon an olefin with an acid salt of a hetero-polyacid.

2. Process which comprises reacting at a temperature above about 100C. upon an olefin with an acid alkali salt of a hetero-polyacid.

3. Process which comprises reacting at a temperature of about 130 C. to about 200 C. upon an olefin with an acid alkali salt of a hetero-polyacid.

4. Process which comprises reacting at a temperature of about 130 C. to about 200 C. at elevated pressure upon an olefin with an acid alkali salt of a hetero-polyacid.

5. Process which comprises reacting at a temperature of about C. and a pressure of about 15 atmospheres upon isobutylene with an acid sodium salt of phospho-tungstic acid in which 3 of the l acid hydrogen atoms of the phosphoe tungstic acid are substituted by sodium.

momma MICHEL. LU'DWIG MULLER. 

